Sverker Hansson

The mechanism of nucleophilic addition to η3-allylpalladium complexes: the influence of ligands on rates and regiochemistry☆

Abstract The influence of the ligands L in η 3 -(3-methylbutenyl)palladium(L 2 ) complexes on the rates and regiochemistry of nucleophilic addition has been studied. Acceptor ligands such as phosphines and 1,5-cyclooctadiene have been found to increase the rate of addition as well as the preference for reaction at the more substituted allyl terminus. There is a good correlation between the rates and the 13 C NMR shifts of the more substituted η 3 -allyl terminus, indiating that the NMR shifts can be used to predict acceptor properties of the ligands. There is a fair agreement between the rates and the regiochemistry of the palladium catalyzed nucleophilic displacement of allylic acetate from these complexes and those for the stoichiometric reactions involving η 3 -allyl complexes.

Palladium-catalyzed allylic acetoxylation: an exploratory study of the influence of added acids

Abstract In order to investigate the possibility of improving the selectivity in palladium-catalyzed acetoxylation of substituted cycloalkenes and linear alkenes, the influence of added strong acids has been studied. It was found that the product selectivity can be increased in some cases, but also that side reactions lower the total yields when trifluoroacetic or stronger acids are used. The improvement of the selectivity may possibly be due to a change in mechanism for the acetoxylation.

A NEW ROUTE TO SYNTHESIZE 2,9-DICARBONITRILE-1,10-PHENANTHROLINE

Abstract A simple, straightforward method to synthesize 2,9-dicarbanitrile-1, 10-phenanthroline from 2,9-dimethyl-1, 10-phenanthroline via 2,9-dicarbamoyl-1, 10-phenanthroline is described.